Table Of ContentPolymers in Sensors
In Polymers in Sensors; Akmal, N., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1998.
In Polymers in Sensors; Akmal, N., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1998.
ACS SYMPOSIUM SERIES 690
Polymers in Sensors
Theory and Practice
Naim Akmal, EDITOR
Union Carbide Technical Center
Arthur M. Usmani, EDITOR
Usmani Development Company
Developed from a symposium sponsored by the
Division of Industrial and Engineering Chemistry
at the 212th National Meeting
of the American Chemical Society,
Orlando, Florida,
August 25-29, 1996
American Chemical Society, Washington, DC
In Polymers in Sensors; Akmal, N., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1998.
Library of Congress Cataloging-in-Publication Data
Polymers in Sensors : theory and practice / Naim Akmal, editor, Arthur M.
Usmani, editor
p. cm.—(ACS symposium series, ISSN 0097-6156; 690)
"Developed from a symposium sponsored by the Division of Industrial and
Engineering Chemistry at the 212th National Meeting of the American Chemical
Society, Orlando, Florida, August 25-29, 1996."
Includes bibliographical references and indexes.
ISBN 0-8412-3550-3
1. Chemical detectors—Congresses. 2. Biosensors—Congresses.
3. Polymers—Congresses.
I. Akmal, Naim, 1962- . II. Usmani, Arthur M, 1940- . III. American
Chemical Society. Division of Industrial and Engineering Chemistry.
IV. American Chemical Society. Meeting (212th : 1996: Orlando, Fla.) V. Series.
TP159.C46P66 1997
681'.2—dc21 98-13989
CIP
This book is printed on acid-free, recycled paper.
Copyright © 1998 American Chemical Society
Distributed by Oxford University Press
All Rights Reserved. Reprographic copying beyond that permitted by Sections 107 or 108 of the U.S.
Copyright Act is allowed for internal use only, provided that a per-chapter fee of $20.00 plus $0.25 per
page is paid to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA.
Republication or reproduction for sale of pages in this book is permitted only under license from ACS.
Direct these and other permissions requests to ACS Copyright Office, Publications Division, 1155 16th
Street, N.W., Washington, DC 20036.
The citation of trade names and/or names of manufacturers in this publication is not to be construed as
an endorsement or as approval by ACS of the commercial products or services referenced herein; nor
should the mere reference herein to any drawing, specification, chemical process, or other data be
regarded as a license or as a conveyance of any right or permission to the holder, reader, or any other
person or corporation, to manufacture, reproduce, use, or sell any patented invention or copyrighted
work that may in any way be related thereto. Registered names, trademarks, etc., used in this
publication, even without specific indication thereof, are not to be considered unprotected by law.
PRINTED IN THE UNITED STATES OF AMERICA
In Polymers in Sensors; Akmal, N., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1998.
Advisory Board
ACS Symposium Series
Mary E. Castellion Omkaram Nalamasu
ChemEdit Company AT&T Bell Laboratories
Arthur B. Ellis Kinam Park
University of Wisconsin at Madison Purdue University
Jeffrey S. Gaffney Katherine R. Porter
Argonne National Laboratory Duke University
Gunda I. Georg
Douglas A. Smith
University of Kansas
The DAS Group, Inc.
Lawrence P. Klemann
Martin R. Tant
Nabisco Foods Group
Eastman Chemical Co.
Richard N. Loeppky
Michael D. Taylor
University of Missouri
Parke-Davis Pharmaceutical
Research
Cynthia A. Maryanoff
R. W. Johnson Pharmaceutical
Research Institute Leroy B. Townsend
University of Michigan
Roger A. Minear
University of Illinois William C. Walker
at Urbana-Champaign DuPont Company
In Polymers in Sensors; Akmal, N., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1998.
Foreword
THE ACS SYMPOSIUM SERIES was first published in 1974 to provide
a mechanism for publishing symposia quickly in book form. The pur
pose of the series is to publish timely, comprehensive books devel
oped from ACS sponsored symposia based on current scientific re
search. Occasionally, books are developed from symposia sponsored
by other organizations when the topic is of keen interest to the chem
istry audience.
Before agreeing to publish a book, the proposed table of contents
is reviewed for appropriate and comprehensive coverage and for in
terest to the audience. Some papers may be excluded in order to better
focus the book; others may be added to provide comprehensiveness.
When appropriate, overview or introductory chapters are added.
Drafts of chapters are peer-reviewed prior to final acceptance or re
jection, and manuscripts are prepared in camera-ready format.
As a rule, only original research papers and original review pa
pers are included in the volumes. Verbatim reproductions of previ
ously published papers are not accepted.
ACS BOOKS DEPARTMENT
In Polymers in Sensors; Akmal, N., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1998.
Preface
THE FIELD OF SENSING TECHNOLOGY covers a vast area of expertise
and application in various arenas. The sensor is a logical element in the infor
mations-acquisition chain. Sensors provide information about our physical,
chemical, and biological environments. The rapid growth in technology and its
application has created a major market for various kinds of sensing devices to
maintain the high quality of the final product and simultaneously to increase the
yield.
There is no doubt that chemical sensors and biosensors are fast-moving,
critical technologies for industrial and biomedical marks. Sensors find wide ap
plications in medicine (for example, blood chemistry determinations and immu
nological and microbiological testing), food, agriculture, and environmental and
industrial monitoring. The value of the industrial gas sensor industry is projected
to more than double by 1998, with semiconductor sensors and electrochemical
sensors leading the way. The total market for worldwide chemical sensors was
$700 million in 1994. This market is growing at an estimated rate of 9.0% per
annum. Also, efforts to reduce the risk of cross-contamination and physician li
ability risks are opening up opportunities for the manufacturers of disposable
biomedical sensors.
The symposium was organized to address the latest developments in sens
ing technology and its application in various industries. This volume presents
the missing link in chemical and biosensing technology and improvements per
formed in recent years. The chapters cover a wide arena of sensors used in
chemical and other related industries.
The chapters in this book have been divided into four sections: diagnostics
and biosensors, gas sensors and their applications, ISE and polymer-based sen
sors and biosensors, and fiber optic sensors. Chapter 1 provides an overview of
the diagnostic section that has not been covered in any other chapter. Chapters
2-7 deal with biosensors and their biomedical applications. Chapters 8-17 pro
vide excellent information pertaining to various gas-sensing technologies for
process industries. Chapters 18-21 provide an overview of the applications of
polymers in sensing technology. A separate section, chapters 22-23, has been
allotted to fiber optic sensors.
This book should be useful to chemists, biochemists, chemical engineers,
process engineers, polymer scientists, and materials scientists. It provides a good
xi
In Polymers in Sensors; Akmal, N., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1998.
source of information to anyone interested in learning about gas sensors—their
chemistry and their limitations. Scientists interested in doing research and de
velopment work in diagnostics and biosensors can take advantage of the book's
broad coverage of sensing technology.
Acknowledgments
We sincerely thank all those who contributed to the successful publication of
this volume. We express our appreciation to Teledyne Electronic Technologies
and Usmani Development Company (UDC) for their support. Also we acknowl
edge the support provided by the staff of ACS Books. The gracious support of
our families is most warmly acknowledged.
NAIM AKMAL
Union Carbide Technical Center
3200 Kanawha Turnpike
South Charleston, WV 25303
ARTHUR M. USMANI
Usmani Development Company
7318 Normandy Way
Indianapolis, IN 46278
xii
In Polymers in Sensors; Akmal, N., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1998.
Chapter 1
An Overview of Medical Polymers and Diagnostic
Reagents
Naim Akmal1 and A. M. Usmani2
1Union Carbide Technical Center, 3200 Kanawha Turnpike,
South Charleston, WV 25303
2Usmani Development Company, 7318 Normandy Way, Indianapolis, IN 46278
This work describes the principles and biochemical reactions involved
in diagnostic reagents, dry chemistry construction and recent advances
in biosensors. Among all the methods and techniques available to date
for the accurate and fast detection of blood sugar and cholesterol, dry
chemistry is still the number one choice. Blood glucose test strips are
made up of suitable enzymes along with indicators such as 3,3'-5,5'-
tetramethylbenzidine in the form of a thin film and layered over a
plastic film. Importance and selection of polymer binders which play a
major role in dry chemistry has been discussed along with the thermal
analysis data and its role for various diagnostic enzymes.
Biosensors using enzyme, GOD for monitoring glucose and the
use of long chain polymers to wire the enzyme to the electrode, in order
to have fast electron movement is also discussed.
Purified enzymes are invariably used in medical diagnostic reagents and in the
measurement of analytes in urine, plasma, serum or whole blood. There has been a
steady growth of dry chemistry during the past three decades. It has surpassed wet
clinical analysis in the number of tests performed in hospitals, laboratories and homes
because of its ease, reliability and accuracy.
Enzymes are specific catalysts that can be derived from plant and animal
tissues; however fermentation continues to be the most popular method. Enzymes are
extensively used in diagnostics, immunodiagnostics, and biosensors. They measure or
amplify signals of many specific metabolites. Purified enzymes are expensive and
2 ©1998 American Chemical Society
In Polymers in Sensors; Akmal, N., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1998.
3
their use for a large number of analytes can be expensive. This is the main reason for
the increasing use of reusable immobilized enzymes in clinical analyses.
Wet chemistry methods for analysis of body analytes, e.g., blood glucose or
cholesterol requires equipment and trained analysts. Millions of people with diabetes
check their blood glucose levels and are able to obtain results in a matter of a few
minutes. However, science has not yet invented an insulin delivery system that can
respond to the body's senses. Injected insulin does not automatically adjust and,
therefore, the dose required to mimic the body's response must be adjusted daily or
even hourly depending on the diet and physical activity. Self-monitoring of blood
glucose levels is essential for diabetics. This has become possible since the last 30
years due to the advent of dry chemistry (1-8). Accurate monitoring of blood glucose
level by an expectant woman will enable her to have normal pregnancy and give birth
to a healthy child. Athletes with diabetes can self-test their blood glucose levels to
avoid significant health problems. Dry chemistries are useful not only to diabetes, but
also to patients with other medical problems. They are also used in animal diagnosis,
food evaluation, fermentation, agriculture, and environmental and industrial
monitoring (1).
Biochemical Reactions
Biochemical reactions for assaying cholesterol and glucose are shown below:
Cholesterol
Cholesterol esterase
Cholesterol esters + H0 > Cholesterol + Fatty acids
2
, , _ Cholesterol oxidase „ _, _
Λ
Cholesterol + 0 > Cholest-4-en-3-one + H0
2 2 2
H0+ chromogen —Peroxidase ^ Dy + H0
2 2 e 2
Notes: (l)End-point followed by dye formation.
(2) Amount of oxygen consumed can be measured amperometrically by an oxygen-sensing
electrode.
(3) The H0 produced by cholesterol oxidase requires phenol to produce dye. A popular
2 2
alternative step is to substitute p-hydroxybenzenesulfonate for phenol in the reaction with
pyridine nucleotide. The subsequent reaction is as follows:
catalase
H0 + ethanol > acetaldehyde +2H0
2 2 2
Acetaldehyde + NAD(P)+ > tate + H+ + NAD(P)H
ace
(4) Free cholesterol determined, if cholesterol esterase omitted.
Glucose
(1) Glucose + 0 + H0 Glucose oxida*e > Gluconic acid + H0
2 2 2 2
H0 + Chromogen —Peroxidase Dye + H0
2 2 > 2 2
Note: Formation of dye.
(2) Glucose + 0 + H0 > Gluconic acid + H0
2 2 2 2
Note: The rate of oxygen depletion is measured with an oxygen electrode.
Two additional steps prevent the formation of oxygen from H0 and are
2 2
as follows.
In Polymers in Sensors; Akmal, N., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1998.